CN110483581B - Palladium complex containing diphosphine m-carborane ligand and preparation and application thereof - Google Patents

Palladium complex containing diphosphine m-carborane ligand and preparation and application thereof Download PDF

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CN110483581B
CN110483581B CN201910734713.3A CN201910734713A CN110483581B CN 110483581 B CN110483581 B CN 110483581B CN 201910734713 A CN201910734713 A CN 201910734713A CN 110483581 B CN110483581 B CN 110483581B
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姚子健
陈静
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    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
    • B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
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Abstract

The invention relates to a palladium complex containing diphosphine m-carborane ligand and preparation and application thereof, wherein the preparation method of the palladium complex comprises the following steps: 1) adding the n-BuLi solution into the meta-carborane solution, and then reacting for 30-60min at room temperature; 2) adding diphenyl phosphorus chloride, and reacting for 3-6h at room temperature; 3) adding PdCl2Reacting at room temperature for 3-5h, and carrying out post-treatment to obtain a palladium complex; the palladium complex is used for catalyzing the reaction of halogenated hydrocarbon and carbon dioxide to synthesize carboxylic acid. Compared with the prior art, the synthesis process is simple and green, and has excellent selectivity and higher yield; the palladium complex has stable physical and chemical properties, and is used as catalyst and halogenated hydrocarbonSubstrates are dissolved in toluene together, and carbon dioxide is introduced under normal pressure for reaction, so that the corresponding carboxylic acid can be synthesized with high yield.

Description

Palladium complex containing diphosphine m-carborane ligand and preparation and application thereof
Technical Field
The invention belongs to the technical field of synthetic chemistry, and relates to a palladium complex containing diphosphine m-carborane ligand, and preparation and application thereof.
Background
Carborane (C)2B10H12) Is a kind of material with special electronic effect,The cage-like compounds with bulky steric hindrance and aromaticity have good chemical and thermal stability, and thus are widely applied to material science, pharmaceutical chemistry and coordination chemistry. Metal complexes based on carborane ligands are generally more stable because the large steric hindrance of the carborane cages stabilizes the metal center, and thus a wide variety of functionalized carborane ligands are synthesized and studied for related reactivity.
The invention develops a novel palladium complex containing diphosphine carborane ligand, and experimental results show that the palladium complex can efficiently catalyze halohydrocarbon to react with carbon dioxide to prepare carboxylic acid, and avoids the reaction of Grignard reagent sensitive to air and water with carbon dioxide, thereby greatly reducing the severity of the reaction.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a palladium complex containing diphosphine carborane ligand, and preparation and application thereof. The preparation method of the palladium complex is simple and green, the obtained divalent palladium complex can efficiently catalyze the reaction of the halohydrocarbon and the carbon dioxide to prepare the carboxylic acid, can catalyze more types of substrates, has good universality, high catalysis efficiency, less byproducts and lower cost, and the product is easy to separate and does not generate a large amount of waste residues. And the palladium complex serving as the catalyst has high stability and is insensitive to air and water.
The purpose of the invention can be realized by the following technical scheme:
a palladium complex containing diphosphine m-carborane ligand, the structural formula of the palladium complex is shown as follows:
Figure RE-GDA0002229410340000021
wherein "·" is a boron hydrogen bond.
A preparation method of a palladium complex containing diphosphine m-carborane ligand comprises the following steps:
1) adding the n-BuLi solution into the meta-carborane solution, and then reacting for 30-60min at room temperature;
2) adding diphenyl phosphorus chloride, and reacting for 3-6h at room temperature;
3) adding PdCl2Reacting at room temperature for 3-5h, and carrying out post-treatment to obtain the palladium complex.
Further, in the step 1), the n-BuLi solution is n-hexane solution of n-BuLi (n-butyllithium), and the m-carborane solution is m-carborane (m-C)2B10H10) A tetrahydrofuran solution of (1).
Further, the step 1) is specifically as follows:
1-1) dropwise adding the n-BuLi solution into the meta-carborane solution at a temperature of between 80 ℃ below zero and 75 ℃ below zero, and then continuously stirring for 25 to 35 min;
1-2) heating to room temperature, and continuing to react for 30-60 min.
Further, in step 3), the post-processing process is as follows: and standing and filtering after the reaction is finished, decompressing and pumping out the solvent to obtain a crude product, and then carrying out column chromatography separation on the crude product.
Further, in the process of column chromatography separation, an eluent is a mixed solvent of dichloromethane and ethyl acetate, and the volume ratio of the dichloromethane to the ethyl acetate is 3-6: 1.
Further, the n-BuLi, the m-carborane, the diphenyl phosphorus chloride and the PdCl2The molar ratio of (2.1-2.5) to (1: 2: 1).
The application of a palladium complex containing diphosphine m-carborane ligand is used for catalyzing halogenated hydrocarbon and carbon dioxide to react to synthesize carboxylic acid.
The specific application method is as follows: the palladium complex is used as a catalyst, halogenated hydrocarbon is used as a substrate, the palladium complex and the halogenated hydrocarbon are dissolved in toluene, carbon dioxide is introduced under normal pressure, the reaction is carried out for 6 to 10 hours at the temperature of between 50 and 80 ℃, and then the reaction liquid is acidified, concentrated and separated by column chromatography, thus the corresponding carboxylic acid can be synthesized with high yield.
Further, the halogenated hydrocarbon comprises one or more of chlorobenzene, 1-bromonaphthalene, p-methyl chlorobenzene, p-dimethylaminobromobenzene, p-nitrochlorobenzene, p-dibromobenzene, m-trimethyliodobenzene, m-aminoiodobenzene or o-methoxybromobenzene.
Further, the molar ratio of the palladium complex to the halogenated hydrocarbon is 0.01-0.03: 1.0.
The invention takes meta-carborane as a raw material, and the meta-carborane is mixed with n-BuLi, diphenyl phosphorus chloride and PdCl2The palladium complex containing diphosphine carborane ligand is obtained by a one-pot method, and the synthesis process is simple and green, and has excellent selectivity and high yield. The palladium complex has stable physical and chemical properties, is taken as a catalyst, takes halohydrocarbon as a substrate, is dissolved in toluene together, and is introduced with carbon dioxide for reaction under normal pressure, so that the corresponding carboxylic acid can be synthesized with high yield.
Compared with the prior art, the invention has the following characteristics:
1) the preparation method of the palladium complex containing diphosphine carborane ligand is simple and green, and has high yield;
2) the palladium complex containing diphosphine carborane ligand has stable physicochemical property and can stably exist in the air;
3) the palladium complex containing diphosphine carborane ligand has higher catalytic activity under mild conditions, can catalyze halohydrocarbon to react with carbon dioxide to synthesize carboxylic acid, and has the advantages of mild reaction conditions, cheap and easily obtained raw materials and high yield (89-96%).
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
Example 1:
synthesis of palladium complex Pd containing diphosphine carborane ligand:
Figure RE-GDA0002229410340000031
at-78 ℃ under stirring n-BuLi(1.6M) solution of n-hexane (1.6mmol) was slowly added dropwise to the o-carborane-containing M-C2B10H10(0.70mmol) in tetrahydrofuran, stirred at this temperature for 30 minutes, slowly warmed to room temperature and allowed to continue to react for 1 hour, then diphenylphosphoryl chloride (1.40mmol) was added and allowed to continue to react at room temperature for 5 hours. Then PdCl is added2(0.70mmol) was added to the reaction system and reacted for an additional 5 hours. After the reaction, the reaction mixture was allowed to stand and filtered, and the solvent was dried under reduced pressure, and the obtained crude product was subjected to column chromatography (dichloromethane/ethyl acetate: 5:1) to obtain a brown target product, palladium complex Pd (yield 81%).
1H NMR(400MHz,CDCl325 ℃ C., (delta) 8.19 to 8.03(m,8H),7.60 to 7.51(m,4H), 7.46 to 7.35(m,8H),3.05 to 2.20(br,10H)26B10H30Cl2P2Pd: c45.26, H4.38; experimental values: c45.29, H4.32.
Example 2:
the palladium complex is used for catalyzing and synthesizing carboxylic acid:
Figure RE-GDA0002229410340000041
in a reaction tube, adding palladium complex [ Pd](0.01mmol) and chlorobenzene (1.0mmol) were dissolved in 3mL of toluene in CO2Pumping and exchanging gas for three times in atmosphere, and connecting with CO at normal pressure2Balloon reaction at 80 deg.c for 8 hr, acidification, concentration of the reaction liquid, and column chromatographic separation to obtain corresponding product C7H6O2(yield 93%),1H NMR(400 MHz,CDCl3,25℃):δ＝8.13(d,J＝7.2Hz,2H),7.63(t,J＝7.6Hz,1H),7.49(t,J＝ 7.6Hz,2H)。HRMS(ESI):calcd for C7H7O2[M+H]+123.0446,found 123.0451。
example 3:
the palladium complex is used for catalyzing and synthesizing carboxylic acid:
Figure RE-GDA0002229410340000042
in a reaction tube, adding palladium complex [ Pd](0.02mmol) and 1-bromonaphthalene (1.0mmol) were dissolved in 3mL of toluene in CO2Pumping and exchanging gas for three times in atmosphere, and connecting with CO at normal pressure2Balloon reaction at 50 deg.c for 10 hr, acidification, concentration of the reaction liquid, and column chromatographic separation to obtain corresponding product C11H8O2(yield 91%),1H NMR (400MHz,CDCl3,25℃):δ＝12.5(brs,1H),8.89(d,J＝8.0Hz,1H),8.22-8.16(m, 2H),7.95(d,J＝8.0Hz,1H),7.65(td,J＝6.8and 1.5Hz,1H),7.55-7.43(m,2H)。 HRMS(ESI):calcd for C11H9O2[M+H]+173.0603,found 173.0601。
example 4:
the palladium complex is used for catalyzing and synthesizing carboxylic acid:
Figure RE-GDA0002229410340000043
in a reaction tube, adding palladium complex [ Pd](0.03mmol) and p-methylchlorobenzene (1.0mmol) were dissolved in 3mL of toluene in CO2Pumping and exchanging gas for three times in atmosphere, and connecting with CO at normal pressure2Balloon reaction at 60 deg.c for 8 hr, acidification, concentration of the reaction liquid, and column chromatographic separation to obtain corresponding product C8H8O2(yield 92%),1H NMR (400MHz,DMSO-d6,25℃):δ＝12.80(s,1H),7.84(d,J＝8.1Hz,2H),7.30(d,J＝8.0 Hz,2H),2.37(s,3H)。HRMS(ESI):calcd for C8H9O2[M+H]+137.0603,found 137.0608。
example 5:
the palladium complex is used for catalyzing and synthesizing carboxylic acid:
Figure RE-GDA0002229410340000051
in a reaction tube, adding palladium complex [ Pd](0.02mmol) and p-dimethylaminobromobenzene (1.0mmol) were dissolved in 3mL of toluene and reacted in CO2Pumping and exchanging air for three times under atmosphere and connecting under normal pressureFeeding CO2Balloon reaction at 50 deg.c for 8 hr, acidification, concentration of the reaction liquid, and column chromatographic separation to obtain corresponding product C9H11NO2(yield 90%),1H NMR(400MHz,DMSO-d6,25℃):δ＝12.71(s,1H),7.77(d,2H),6.70(d,2H), 2.98(s,6H)。HRMS(ESI):calcd for C9H12NO2[M+H]+166.0868,found 166.0862。
example 6:
the palladium complex is used for catalyzing and synthesizing carboxylic acid:
Figure RE-GDA0002229410340000052
in a reaction tube, adding palladium complex [ Pd](0.01mmol) and p-nitrochlorobenzene (1.0mmol) were dissolved in 3mL of toluene in CO2Pumping and exchanging gas for three times in atmosphere, and connecting with CO at normal pressure2Balloon reaction at 60 deg.c for 10 hr, acidification, concentration of the reaction liquid, and column chromatographic separation to obtain corresponding product C7H5NO4(yield 96%),1H NMR (400MHz,DMSO-d6,25℃):δ＝13.64(s,1H),8.33–8.30(m,2H),8.20–8.13(m,2H)。 HRMS(ESI):calcd for C7H6NO4[M+H]+168.0297,found 168.0295。
example 7:
the palladium complex is used for catalyzing and synthesizing carboxylic acid:
Figure RE-GDA0002229410340000053
in a reaction tube, adding palladium complex [ Pd](0.03mmol) and p-dibromobenzene (1.0mmol) were dissolved in 3mL of toluene and reacted in CO2Pumping and exchanging gas for three times in atmosphere, and connecting with CO at normal pressure2Balloon reaction at 60 deg.c for 8 hr, acidification, concentration of the reaction liquid, and column chromatographic separation to obtain corresponding product C8H6O4(yield 95%),1H NMR (400MHz,DMSO-d6,25℃):δ＝12.71(s,1H),8.03(d,4H)。HRMS(ESI):calcd for C8H7O4[M+H]+167.0344,found 167.0346。
example 8:
the palladium complex is used for catalyzing and synthesizing carboxylic acid:
Figure RE-GDA0002229410340000061
in a reaction tube, adding palladium complex [ Pd](0.03mmol) and m-trimethyliodobenzene (1.0mmol) were dissolved in 3mL of toluene in CO2Pumping and exchanging gas for three times in atmosphere, and connecting with CO at normal pressure2Balloon reaction at 80 deg.c for 8 hr, acidification, concentration of the reaction liquid, and column chromatographic separation to obtain corresponding product C10H12O2(yield 89%),1H NMR (400MHz,CDCl3,25℃):δ＝9.85(br s,1H),6.92(s,2H),2.45(s,6H),2.32(s,3H)。 HRMS(ESI):calcd for C10H13O2[M+H]+165.0916,found 165.0920。
example 9:
the palladium complex is used for catalyzing and synthesizing carboxylic acid:
Figure RE-GDA0002229410340000062
in a reaction tube, adding palladium complex [ Pd](0.01mmol) and m-Aminoiodobenzene (1.0mmol) were dissolved in 3mL of toluene in CO2Pumping and exchanging gas for three times in atmosphere, and connecting with CO at normal pressure2Balloon reaction at 60 deg.c for 10 hr, acidification, concentration of the reaction liquid, and column chromatographic separation to obtain corresponding product C7H7NO2(yield 92%),1H NMR (400MHz,DMSO-d6,25℃):δ＝7.18-7.16(m,1H),7.12-7.07(m,2H),6.76(dt,J＝ 7.0and 2.1Hz,1H),5.37(br s,2H)。HRMS(ESI):calcd for C7H8NO2[M+H]+ 138.0555,found 138.0558。
example 10:
the palladium complex is used for catalyzing and synthesizing carboxylic acid:
Figure RE-GDA0002229410340000063
in a reaction tube, adding palladium complex [ Pd](0.03mmol) and o-methoxybromobenzene (1.0mmol) were dissolved in 3mL of toluene and reacted in CO2Pumping and exchanging gas for three times in atmosphere, and connecting with CO at normal pressure2Balloon reaction at 60 deg.c for 8 hr, acidification, concentration of the reaction liquid, and column chromatographic separation to obtain corresponding product C8H8O3(yield 91%),1H NMR (400MHz,CDCl3,25℃):δ＝10.20(br s,1H),8.10(d,J＝7.4Hz,1H),7.54(t,J＝7.4 Hz,1H),7.08(t,J＝7.4Hz,1H),7.03(d,J＝8.5Hz,1H),4.03(s,3H)。HRMS(ESI): calcd for C8H9O3[M+H]+153.0552,found 153.0549。
example 11:
a palladium complex containing diphosphine m-carborane ligand, the structural formula of the palladium complex is shown as follows:
Figure RE-GDA0002229410340000071
wherein "·" is a boron hydrogen bond.
The preparation method of the palladium complex comprises the following steps:
1) adding n-BuLi normal hexane solution into a tetrahydrofuran solution of m-carborane at the temperature of-80 ℃, and then continuously stirring for 35 min; heating to room temperature, and continuing to react for 30 min;
2) adding diphenyl phosphorus chloride, and reacting for 6 hours at room temperature;
3) adding PdCl2And reacting at room temperature for 3h, standing and filtering after the reaction is finished, decompressing and pumping out the solvent to obtain a crude product, and then carrying out column chromatography separation on the crude product to obtain the palladium complex. Wherein, in the process of column chromatography separation, the eluent is a mixed solvent of dichloromethane and ethyl acetate, and the volume ratio of the dichloromethane to the ethyl acetate is 6: 1. n-BuLi, m-carborane, diphenylphosphoryl chloride and PdCl2In a molar ratio of 2.1:1:2: 1.
The palladium complex is used for catalyzing halogenated hydrocarbon to react with carbon dioxide to synthesize carboxylic acid. The molar ratio of palladium complex to halogenated hydrocarbon was 0.03: 1.0.
Example 12:
a palladium complex containing diphosphine m-carborane ligand, the structural formula of the palladium complex is shown as follows:
Figure RE-GDA0002229410340000081
wherein "·" is a boron hydrogen bond.
The preparation method of the palladium complex comprises the following steps:
1) adding n-BuLi normal hexane solution into a tetrahydrofuran solution of m-carborane at-75 ℃, and then continuously stirring for 25 min; heating to room temperature, and continuing to react for 60 min;
2) adding diphenyl phosphorus chloride, and reacting for 3 hours at room temperature;
3) adding PdCl2And reacting at room temperature for 5h, standing and filtering after the reaction is finished, decompressing and pumping out the solvent to obtain a crude product, and then carrying out column chromatography separation on the crude product to obtain the palladium complex. Wherein, in the process of column chromatography separation, the eluent is a mixed solvent of dichloromethane and ethyl acetate, and the volume ratio of the dichloromethane to the ethyl acetate is 3:1. n-BuLi, m-carborane, diphenylphosphoryl chloride and PdCl2In a molar ratio of 2.5:1:2: 1.
The palladium complex is used for catalyzing halogenated hydrocarbon to react with carbon dioxide to synthesize carboxylic acid. The molar ratio of the palladium complex to the halogenated hydrocarbon was 0.01: 1.0.
Example 13:
a palladium complex containing diphosphine m-carborane ligand, the structural formula of the palladium complex is shown as follows:
Figure RE-GDA0002229410340000082
wherein "·" is a boron hydrogen bond.
The preparation method of the palladium complex comprises the following steps:
1) adding n-BuLi normal hexane solution into a tetrahydrofuran solution of m-carborane at the temperature of-77 ℃, and then continuously stirring for 30 min; heating to room temperature, and continuing to react for 45 min;
2) adding diphenyl phosphorus chloride, and reacting for 4 hours at room temperature;
3) adding PdCl2Reacting at room temperature for 4h, standing and filtering after the reaction is finished, decompressing and pumping out the solvent to obtain a crude product, and then carrying out column chromatography separation on the crude product to obtain the palladium complex. Wherein, in the process of column chromatography separation, the eluent is a mixed solvent of dichloromethane and ethyl acetate, and the volume ratio of the dichloromethane to the ethyl acetate is 5: 1. n-BuLi, m-carborane, diphenylphosphoryl chloride and PdCl2In a molar ratio of 2.3:1:2: 1.
The palladium complex is used for catalyzing halogenated hydrocarbon to react with carbon dioxide to synthesize carboxylic acid. The molar ratio of palladium complex to halogenated hydrocarbon was 0.02: 1.0.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A palladium complex containing diphosphine m-carborane ligand is characterized in that the structural formula of the palladium complex is as follows:
Figure FDA0002820787570000011
wherein "·" is a boron hydrogen bond.
2. A process for the preparation of a palladium complex with a bis-phosphine carborane ligand according to claim 1, comprising the steps of:
1) adding the n-BuLi solution into the meta-carborane solution, and then reacting for 30-60min at room temperature;
2) adding diphenyl phosphorus chloride, and reacting for 3-6h at room temperature;
3) adding PdCl2Reacting at room temperature for 3-5h, and carrying out post-treatment to obtain the palladium complex.
3. The method for preparing a palladium complex containing diphosphine carborane ligand according to claim 2, wherein in the step 1), the n-BuLi solution is n-hexane solution of n-BuLi, and the m-carborane solution is tetrahydrofuran solution of m-carborane.
4. The preparation method of the palladium complex containing diphosphine m-carborane ligand according to claim 2, wherein the step 1) is specifically as follows:
1-1) dropwise adding the n-BuLi solution into the meta-carborane solution at a temperature of between 80 ℃ below zero and 75 ℃ below zero, and then continuously stirring for 25 to 35 min;
1-2) heating to room temperature, and continuing to react for 30-60 min.
5. The method for preparing a palladium complex containing a diphosphine m-carborane ligand according to claim 2, wherein the post-treatment process in step 3) is as follows: and standing and filtering after the reaction is finished, decompressing and pumping out the solvent to obtain a crude product, and then carrying out column chromatography separation on the crude product.
6. The method for preparing a palladium complex containing diphosphine m-carborane ligand according to claim 5, wherein an eluent is a mixed solvent of dichloromethane and ethyl acetate during the column chromatography separation process, and the volume ratio of dichloromethane to ethyl acetate is 3-6: 1.
7. The process for preparing a palladium complex containing a diphosphine carborane ligand according to claim 2, wherein the n-BuLi, the m-carborane, the diphenylphosphoryl chloride and the PdCl are2The molar ratio of (A) to (B) is 2.1-2.5:1:2: 1.
8. Use of a palladium complex containing a bis-phosphine carborane ligand according to claim 1, wherein said palladium complex is used to catalyze the reaction of a halogenated hydrocarbon with carbon dioxide to produce a carboxylic acid.
9. Use of a palladium complex with a bis-phosphine carborane ligand according to claim 8, wherein said halogenated hydrocarbon comprises one or more of chlorobenzene, 1-bromonaphthalene, p-methylchlorobenzene, p-dimethylaminobromobenzene, p-nitrochlorobenzene, p-dibromobenzene, m-trimethyliodobenzene, m-aminoiodobenzene, or o-methoxybromobenzene.
10. Use of a palladium complex with a bis-phosphine carborane ligand according to claim 8, wherein the molar ratio of palladium complex to halogenated hydrocarbon is 0.01-0.03: 1.0.
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